WO2021101385A1 - Bag-in-container with a coating layer - Google Patents
Bag-in-container with a coating layer Download PDFInfo
- Publication number
- WO2021101385A1 WO2021101385A1 PCT/NL2020/050736 NL2020050736W WO2021101385A1 WO 2021101385 A1 WO2021101385 A1 WO 2021101385A1 NL 2020050736 W NL2020050736 W NL 2020050736W WO 2021101385 A1 WO2021101385 A1 WO 2021101385A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- preform
- container
- bag
- coating layer
- facing surfaces
- Prior art date
Links
- 239000011247 coating layer Substances 0.000 title claims abstract description 131
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000000576 coating method Methods 0.000 claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- 230000008021 deposition Effects 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims description 82
- 239000010410 layer Substances 0.000 claims description 36
- 238000000071 blow moulding Methods 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 31
- -1 fluoroalkyl acrylate Chemical compound 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 238000000151 deposition Methods 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 230000005495 cold plasma Effects 0.000 claims description 7
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 239000012815 thermoplastic material Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- PWRRNECAYDKCHZ-UHFFFAOYSA-N 3-fluoro-2-methylprop-2-enoic acid Chemical compound FC=C(C)C(O)=O PWRRNECAYDKCHZ-UHFFFAOYSA-N 0.000 claims description 3
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 claims description 3
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 235000013305 food Nutrition 0.000 abstract description 5
- 230000032798 delamination Effects 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 230000004888 barrier function Effects 0.000 description 13
- 239000005020 polyethylene terephthalate Substances 0.000 description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 230000009467 reduction Effects 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000000976 ink Substances 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 description 6
- 238000002042 time-of-flight secondary ion mass spectrometry Methods 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- PCIUEQPBYFRTEM-UHFFFAOYSA-N perfluorodecanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F PCIUEQPBYFRTEM-UHFFFAOYSA-N 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 4
- 235000013361 beverage Nutrition 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 4
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 239000000443 aerosol Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 235000013405 beer Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000010017 direct printing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003303 reheating Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- OZCRKDNRAAKDAN-IWQZZHSRSA-N (z)-but-1-ene-1,4-diol Chemical compound OCC\C=C/O OZCRKDNRAAKDAN-IWQZZHSRSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- DGOBMKYRQHEFGQ-UHFFFAOYSA-L acid green 5 Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC(=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 DGOBMKYRQHEFGQ-UHFFFAOYSA-L 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- UYANAUSDHIFLFQ-UHFFFAOYSA-N borinic acid Chemical compound OB UYANAUSDHIFLFQ-UHFFFAOYSA-N 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- SKOLWUPSYHWYAM-UHFFFAOYSA-N carbonodithioic O,S-acid Chemical compound SC(S)=O SKOLWUPSYHWYAM-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000001913 cyanates Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000004941 influx Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 235000008960 ketchup Nutrition 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 150000002905 orthoesters Chemical class 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000004713 phosphodiesters Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- PNVUZMNHWBDJQY-UHFFFAOYSA-N trioxidanylmethane Chemical compound COOO PNVUZMNHWBDJQY-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/62—Plasma-deposition of organic layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B11/00—Making preforms
- B29B11/14—Making preforms characterised by structure or composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/071—Preforms or parisons characterised by their configuration, e.g. geometry, dimensions or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/42—Applications of coated or impregnated materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D77/00—Packages formed by enclosing articles or materials in preformed containers, e.g. boxes, cartons, sacks or bags
- B65D77/04—Articles or materials enclosed in two or more containers disposed one within another
- B65D77/06—Liquids or semi-liquids or other materials or articles enclosed in flexible containers disposed within rigid containers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2201/00—Polymeric substrate or laminate
- B05D2201/02—Polymeric substrate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2451/00—Type of carrier, type of coating (Multilayers)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2701/00—Coatings being able to withstand changes in the shape of the substrate or to withstand welding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C2049/024—Combined blow-moulding and manufacture of the preform or the parison not using inherent heat of the preform, i.e. 2 step blow moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2791/00—Shaping characteristics in general
- B29C2791/001—Shaping in several steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/07—Preforms or parisons characterised by their configuration
- B29C2949/0715—Preforms or parisons characterised by their configuration the preform having one end closed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
- B29C2949/3008—Preforms or parisons made of several components at neck portion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C2949/00—Indexing scheme relating to blow-moulding
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- B29C2949/00—Indexing scheme relating to blow-moulding
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- B29C2949/00—Indexing scheme relating to blow-moulding
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- B29C2949/3032—Preforms or parisons made of several components having components being injected
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
- B29C2949/3064—Preforms or parisons made of several components having at least one components being applied using techniques not covered by B29C2949/3032 - B29C2949/3062
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C2949/00—Indexing scheme relating to blow-moulding
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
- B29C2949/3086—Interaction between two or more components, e.g. type of or lack of bonding
- B29C2949/3094—Interaction between two or more components, e.g. type of or lack of bonding preform having at least partially loose components, e.g. at least partially loose layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/08—Biaxial stretching during blow-moulding
- B29C49/10—Biaxial stretching during blow-moulding using mechanical means for prestretching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
- B29K2023/12—PP, i.e. polypropylene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/003—PET, i.e. poylethylene terephthalate
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/04—Polyesters derived from hydroxycarboxylic acids
- B29K2067/046—PLA, i.e. polylactic acid or polylactide
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0082—Plasma
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/26—Scrap or recycled material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
- B29L2009/001—Layered products the layers being loose
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
- B29L2009/005—Layered products coated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/712—Containers; Packaging elements or accessories, Packages
- B29L2031/7158—Bottles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D2577/00—Packages formed by enclosing articles or materials in preformed containers, e.g. boxes, cartons, sacks, bags
- B65D2577/04—Articles or materials enclosed in two or more containers disposed one within another
- B65D2577/041—Details of two or more containers disposed one within another
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Definitions
- the invention is in the field of containers for foods and drinks, as well as to methods for preparing these containers, and to preforms used in these methods.
- the present invention is directed to these methods and to containers and/or preforms for such containers with a coating layer apphed thereon.
- Such beverage containers can be made of different materials. Owing to their hght weight and strength, polymer materials, such as plastics, in particular thermoplastic materials, are often used for packaging foods and drinks. Suitable polymer materials for food and drinks containers are polyesters, such as polyethylene terephthalate (PET), polylactic acid (PLA), polyethylene 2,5-furandicarboxylate (PEF), and other widely available materials such as polypropylene (PP) and polyethylene (PE).
- PET polyethylene terephthalate
- PLA polylactic acid
- PET polyethylene 2,5-furandicarboxylate
- PP polypropylene
- PE polyethylene
- Containers made of thermoplastic polymers can be produced using blow molding.
- a preform for the container is produced, for instance by injection molding.
- a container is produced by reheating the preform using infrared radiation and stretching the reheated preform into its final shape, typically in a blow molding step (also referred to as stretch blow molding). Transporting empty containers is inefficient. Therefore, preforms for containers are often produced in one location and transported to the next location, where the preforms are blow-molded into their final dimensions and filled.
- containers can be recycled.
- Polymers such as PET, PP, and PE are already recycled to a great extent, and there is a good infrastructure for recycling such materials, which makes it convenient to dispose these materials in a responsible way.
- pure materials i.e., plastics that do not contain many other materials.
- a special type of beverage containers is the bag-in-container.
- This type of container comprises an inner layer i.e. an inner container, or bag, in which a fluid is contained, and an outer layer, i.e. an outer container, which provides the structural integrity to the bag-in-container.
- elevated gas pressure vis-a-vis the atmospheric pressure
- Bag-in-containers are used for instance in draught beer systems. Bag- in-containers can be produced by producing a preform comprising an inner layer, i.e.
- an inner layer of the preform is stretched to become the inner layer of the container, and the outer layer of the preform is stretched to become the outer layer of the container.
- the inner and outer container of a bag-in-container are made from the same material.
- the inner container, or bag delaminates from the outer container during use. This can be achieved by using different materials for the inner and outer container, that do not adhere well to each other.
- using different materials for the inner and the outer preform or container has disadvantages for recycling the container.
- integrally blow molding of the preforms comprising different materials into a bag-in-container can prove difficult, in particular because different materials typically have a different reheating behavior in infrared.
- release agents are applied onto the inner preform to assist delamination. Typically, release agents such as silicone and PTFE are apphed, e.g. sprayed, on the outer surface of the inner preform.
- release agents have the tendency to flow over the surface, resulting in an uneven distribution of release agent over the surface of the inner preform, which may also result in parts of the surface not being covered at all by the release agent.
- release agents may contaminate the surroundings, such as the machines used, and it may interfere with subsequent processing steps, such as welding, and the hke.
- EP2 148770 describes a bag-in-container made from an inner preform and an outer preform of the same material, wherein the inner and outer layers of the container release. Application of a release agent is advantageous in some cases.
- An objective of the present invention is to provide containers having at least one surface treated, wherein the treatment is used for adding various functionalities to the container.
- Another objective of the present invention is to provide coated containers or preforms for containers, which coating can be used to add various functionalities to the container, without adding a large amount of extra material to the container, thereby maintaining good recyclabihty of the container.
- a further objective is to optimize delamination of the inner container and outer container of a bag-in-container, without one or more disadvantages of the methods in the prior art.
- a method for applying a coating layer on a preform for a bag-in-container using plasma deposition In addition, a method for producing a bag-in-container is provided.
- a preform for a bag-in-container comprising an inner layer, i.e. an inner preform, and an outer layer, i.e. an outer preform, with facing surfaces, wherein at least one of the facing surfaces is coated with a coating layer.
- a bag-in-container comprising an in inner layer, i.e. an inner container, and an outer layer, i.e. an outer container, obtainable by integrally blow molding of a preform for a bag-in-container as described herein.
- the inner layer of the preform forms the inner layer of the container upon blow molding.
- the outer layer of the preform forms the outer layer of the container upon blow molding.
- the coating layer is applied to a preform for a bag-in-container using a low-energy atmospheric plasma discharge, resulting in a coating layer which is preferably crosslinked and/or covalently grafted onto the surface of the preform. Surprisingly, the coating layer stays intact during blow molding, i.e. stretching of the preform into a container. Using the method described herein, very thin coating layers can be achieved.
- Another aspect of the invention is the use of plasma deposition in the production of a bag-in-container. More specifically, the present invention seeks to improve bag-in containers or preforms therefor in one or more of the following aspects:
- UV light transmission properties visible or ultraviolet (UV) light
- Figure 1 is a schematic representation of a preform for a container to be used in a bag-in-container according to the invention.
- Figure 2 is a schematic representation of a container obtainable by blow molding of a preform.
- Figure 3 is a schematic representation of a preform for a bag-in container comprising an inner preform and an outer preform, according to an aspect of the invention.
- Figure 4 is a schematic representation of a bag-in-container according to an aspect of the invention.
- Figure 5 shows an example of TOF-SIMS (time-of-flight secondary ion mass spectrometry) analysis on a PET preform, on which a coating layer according to the invention is applied to the top half of the analyzed area.
- TOF-SIMS time-of-flight secondary ion mass spectrometry
- the detected ions are representative for the coating layer.
- Figure 6 shows an example of TOF-SIMS analysis on a PET preform, on which a coating layer according to the invention is applied to the top half of the analyzed area.
- the detected ions are representative for PET.
- Figure 7 shows an example of TOF-SIMS analysis on a container, which container was produced by blow molding of a preform with a coating layer according to the invention applied thereon.
- the detected ions are representative for the coating layer.
- a method for producing a bag-in-container comprises the method for applying a coating layer as described herein, followed by a stretching step.
- a low-energy plasma is defined herein as a plasma of which the power density is high enough to activate the precursors and/or the preform, allowing a chemical reaction to take place, but low enough to prevent destruction of the precursors, the preform and/or the container.
- the power density may be in the range of 0.2 - 8 W/dm 3 , more preferably between 0.5 W/dm 3 and 7 W/dm 3 , still more preferably between 0.8 W/dm 3 and 6 W/dm 3 , yet more preferably between 1 W/dm 3 and 5 W/dm 3 , even more preferably between 1.5 W/dm 3 and 4 W/dm 3 , still even more preferably between 2 W/dm 3 and 3 W/dm 3 , such as 2 W/dm 3 , 2.1 W/dm 3 , 2.2 W/dm 3 , 2.3 W/dm 3 , 2.4 W/dm 3 , 2.5 W/dm 3 , 2.6 W/dm 3 , 2.7 W
- a cold plasma is defined herein as a plasma of which the temperature is sufficiently low to not melt or otherwise damage the precursor and/or preform that are exposed to said cold plasma.
- the temperature of the plasma may be 150 °C or lower, preferably 130 °C or lower, more preferably 100 °C or lower, yet more preferably 70 °C or lower, even more preferably 60 °C or lower, yet more preferably 55 °C or lower, still even more preferably 50 °C or lower, even yet more preferably 45 °C or lower.
- the temperature of the plasma may be as low as room temperature, i.e., the temperature surrounding the plasma.
- room temperature may be in the range of 10-40 °C, preferably 15-30 °C, such as 20-25 °C.
- the temperature of the plasma will generally not be lower than room temperature.
- the optimal temperature may be selected. Hence, in an embodiment the temperature of the plasma is selected taking into account the type of precursor, the precursor mixture and/or the plasma pressure.
- the plasma of the present invention is preferably an atmospheric plasma which has a pressure around ambient pressure.
- Such plasma is created and discharged typically at a pressure of between 400 and 1600 hPa, preferably at a pressure between 450 and 1400, even more preferably at a pressure between 500 and 1300 hPa, yet more preferably between 600 and 1250 hPa, even more preferably between 700 hPa and 1200 hPa, still more preferably between 800 hPa and 1150 hPa, yet more preferably between 900 hPa and 1100 hPa, most preferably about ambient pressure, which is typically about 1013 hPa.
- Pressure of the plasma can play an important role in the quabty of the deposited layer.
- Some plasma precursors are sensitive to too low and/or too high plasma pressures compared to the atmospheric pressure, while other precursors provide a better coating at lower or higher plasma pressures.
- low-energy, cold plasma can typically be apphed under reduced pressure of lower than 400 hPa down to vacuum, or increased pressure of more than 1600 hPa, both types requiring a pressure vessel to maintain such low or high pressures.
- the use of a plasma with pressures in the currently preferred ranges around the ambient pressure reduces costs and difficulties relating to maintaining pressure differences and pressure gradients.
- a plasma with the conditions described above may be referred to as a soft plasma.
- the soft plasma may provide enough energy to activate the precursors, the preform, or both. This allows reactions, such as polymerization reactions to take place between the activated precursors, as well as between the activated precursors and the activated preform.
- the conditions are mild enough to prevent destruction and/or loss of chemical function of the precursors. Therefore, a wide range of precursors may be used in the production of the coating layer. Even sensitive precursors such as antibodies may be activated using the soft, i.e., low- energy, cold plasma.
- the plasma may be generated using a dielectric barrier discharge (DBD plasma), preferably under atmospheric conditions.
- DBD plasma dielectric barrier discharge
- a coating layer as described herein is defined as a layer of a material of a different composition than the substrate onto which it is deposited, i.e., the preform for a container.
- the plasma chemically activates at least one of the precursor(s) and/or the inner and/or outer preform for the bag-in-container.
- This activation of the precursors and/or the preform may occur by opening of double molecular bonds, radical removal and/or ion formation. This allows and/or improves the reactions required to form the coating layer. These reactions may involve:
- the coating layer is covalently bound to the surface.
- the coating layer comprises crosslinks and the coating layer comprises covalent bonds with the preform or the container.
- Such crosslinks and covalent bonds are beheved to be responsible for, or at least to improve, the structural integrity of the coating. If the coating is applied to a preform which is later on in the process increased in size, e.g. by stretch blow molding, the crosslinks and covalent bonds between the coating layer and the preform prevent the coating layer to be damaged, even when the preform is stretched.
- the coating layer stays intact when the preform is stretched, for instance during blow molding, including stretch blow molding.
- crosslinks between the molecules and covalent bonds between the coating layer and the preform prevent the coating layer from being damaged, even when the preform is stretched.
- the preform comprises a thermoplastic material, allowing the preform to be moldable at elevated temperatures.
- the thermoplastic material comprises one or more selected from the group consisting of polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyethylene 2,5-furandicarboxylate (PEF), polyethylene naphthalate (PEN), and polylactic acid (PLA).
- Suitable precursors may comprise at least one moiety selected from the group comprising alkane, alkene, alkyne, benzene derivatives, haloalkane, fluoroalkane, chloroalkane, bromoalkane, iodoalkane, alcohol, ketone, aldehyde, acyl halide, carbonate, carboxylate, carboxylic acid, ester, methoxy, hydroperoxide, peroxide, ether, hemiacetal, hemiketal, acetal, ketal, orthoester, heterocycle, orthocarbonate ester, amide, amines, imine, imide, azide, azo compound, cyanates, nitrate, nitrile, nitrite, nitro compound, nitroso compound, oxime, pyridine derivate, thiol, thioether, disulfide, sulfoxide, sulfone, sulfinic acid, sulfonic
- the precursors are selected from the group consisting of acetylene, tetraethyl orthosilicate (TEOS), cis-butene- 1,4-diol, anti-bodies, polypeptides, precursors for protection against light in the UV and visible region, and combinations thereof.
- TEOS tetraethyl orthosilicate
- cis-butene- 1,4-diol cis-butene- 1,4-diol
- anti-bodies polypeptides
- polypeptides precursors for protection against light in the UV and visible region, and combinations thereof.
- the precursors can be selected from the group consisting of fluoro-acrylate monomers, fluoroalkyl acrylate monomers, fLuoro-methacrylate monomers, fluoro-alkyl methacrylate monomers, fluoro-silane monomers, and combinations and derivatives thereof, and cyclosiloxanes.
- the coating layer is derived from a first precursor comprising fluoro-acrylate monomers, fluoroalkyl acrylate monomers, fluoro-methacrylate monomers, fluoro-alkyl methacrylate monomers, fluoro-silane monomers, or a combination or derivatives thereof, and a second precursor comprising cyclosiloxanes.
- a coating layer which is produced from the above-mentioned precursors may result in a preform with a moisture uptake coefficient lower than 0.050 wt.% per week, relative to the weight of the preform. As a result, the shelf-life of the preform improves considerably, for instance with four weeks or more. This functionality may be achieved using a thin coating layer, which does not give a preform an impression that it is faulty or contaminated.
- the precursors comprise one of the above list of suitable precursors. However, in other embodiments, the precursors comprise two or more of the above list of suitable precursors.
- a method is provided wherein the coating layer is created using at least two precursors, wherein at least one of said precursors is suitable to act as a light -barrier, specifically against ultraviolet (UV) and visible light.
- UV ultraviolet
- the coating layer may have more than one functionality, such as reduced moisture uptake, as well as protection against UV/visible light.
- combining two or more precursors may lead to improved functionalities, such as obtaining an even higher reduction of the moisture uptake coefficient, which could result in moisture uptake coefficients as low as 0.030 wt.% per week or less, relative to the weight of the preform.
- the coating layer may act as a barrier against gases.
- the coating layer acts as a barrier against oxygen (O2) and/or carbon dioxide (CO2).
- O2 oxygen
- CO2 carbon dioxide
- Migration of gases such as O2 towards the inside of a bag-in-container may cause degradation of the contents of the bag-in-container.
- Outward migration of gases such as CO2 may also result in a decrease in quality of the contents, for example in the case of carbonated drinks.
- the coating layer imparts one or more functionalities to the preform for a bag-in-container.
- the functionalities imparted by the coating layer may be present both on the preform before stretching, and on the bag-in-container, after performing the stretching step.
- Such functionalities may be related to one or more of the following properties:
- barrier properties against e.g. permeation of gases, such as O2 and/or CO2 , as well as against other undesired chemicals;
- - optical properties e.g. addition of color or fluorescence, and/or providing a barrier against ultraviolet or visible light; - reheat properties;
- the functionality of the coating layer is at least partially determined by the type of precursors which are used to make the coating layer. Table 1 summarizes which precursor types and/or specific precursors may be used in order to impart certain functionalities, as observed in experiments by the inventors.
- One function of a coating layer may be to reduce the moisture uptake rate of a coated preform, prior to increasing the preform to a full- sized bag-in-container, e.g. by stretch blow molding.
- the plasma deposited coating layer can result in a preform with a better stretch blow molding ability compared to the currently employed methods.
- reproducibihty is extremely important.
- Better stretch blow molding ability allows to increase the reproducibihty of the production of plastic containers from preforms.
- the coating layer may result in a reduction of the moisture uptake rate, thereby improving the shelf-life of the preform.
- Increased storage time is advantageous for several reasons.
- the production of the bag-in-containers from preforms, whereby the preforms are produced in a separate process, can be hampered due to many different reasons, e.g. breakdown of one or more machines, national holidays whereby the factory has to close down for one or more weeks, striking employees, etc.
- the preforms may need to be transported over long distances with long travelhng times, e.g. by overseas shipment. In these cases, the preforms which are close to their expiration date could be already expired by the time bag-in-containers are produced from the preforms.
- preforms tend to be significantly smaller than the bag-in containers, transportation of preforms is easier and less expensive than transportation of bag-in-containers. Hence, it tends to be cost effective to produce preforms in a specialized facility, and to transport these preforms to a second facility where the bag-in-containers are produced, and possibly also filled and prepared for consumption.
- the moisture uptake rate may already be reduced considerably if only part of the complete surface the preform is treated. For instance, if only the outer surface of the assembled preform comprising the inner and outer preforms is treated, the uptake rate could be approximately halved, and, if the preforms are sealed off from the environment, the moisture uptake rate could be reduced by a factor of 10 or more.
- the preform has a moisture uptake coefficient lower than 0.070 wt.% per week relative to the weight of said preform, preferably lower than 0.050 wt.% per week relative to the weight of the preform, even more preferably lower than 0.040 wt.% per week relative to the weight of the preform, most preferably lower than 0.030 wt.% per week relative to the weight of the preform.
- the currently available methods for the reduction of moisture uptake rate obtain a preform with a moisture uptake coefficient higher than 0.070 wt.% per week relative to the weight of said preform.
- the moisture uptake coefficient has to be lower than 0.070 wt.% per week relative to the weight of said preform.
- a moisture uptake coefficient lower than 0.050 wt.% per week relative to the weight of said preform further increases the shelf-life of the preform.
- the present inventors have noticed that by decreasing the moisture uptake coefficient to below 0.070 wt.% per week relative to the weight of said preform, the preform validity increased with a minimum of four weeks. The further reduction of the moisture uptake coefficient, resulted in an even higher minimal increase of the shelf-life.
- the present inventors noted that the reduction of the moisture uptake coefficient to below 0.030 wt.% per week relative to the weight of the preform increased the shelf-life by more than twelve weeks.
- the precursors comprise fluorocarbons, siloxanes, fatty acids and/or hydrocarbons, or any combination thereof, preferably PFDA, HMDSO, TEOS, VEOS, V4D4, nonanoic acid, nonene, dodecane, or any combination thereof. Reduction of the moisture uptake rate has been experimentally observed for such precursors. b. Improved delamination of inner and outer layers
- the precursors comprise fluorocarbons, siloxanes, polymer solutions or any combination thereof, preferably PFDA, EVOH or any combination thereof. Improved delamination has been experimentally observed for such precursors. c. Improved reheat properties
- the precursors comprise metal nanoparticles, carbon nanoparticles, conductive polymers or any combination thereof, preferably Au, CNTs, polyaniline, polythiophene or any combination thereof. Improved heat absorption has been experimentally observed for such precursors. d. Improved slip properties This is particularly important to improve processes wherein the preforms and/or bag-in-containers are conveyed in e.g. a filling fine.
- the precursors comprise fluorocarbons, siloxanes, glycols, hydrocarbons, fatty acids or any combination thereof, preferably PFDA, HMDSO, PEGMEA, DEGEA or any combination thereof. Improved slip between bag-in-containers has been experimentally observed for such precursors. e. Added color and/or other optical properties
- the precursors comprise one or more acrylic inks, UV tracer solutions or any combination thereof, preferably STS inks, radiant UV tracers or any combination thereof. Smooth coloring of the preform or container has been experimentally observed for such precursors. f. Improved CO2 barrier properties
- the precursors comprise siloxanes, polymer solutions or any combination thereof, preferably HMDSO, VEOS, EVOH or any combination thereof.
- Improved CO2 barrier properties have been experimentally observed for such precursors. g. Improved O2 barrier properties
- the precursors comprise siloxanes, polymer solution or any combination thereof, preferably HMDSO, VEOS, V4D4, EVOH or any combination thereof.
- Improved O2 barriers have been experimentally observed for such precursors. h. Improved light barrier properties
- the precursors comprise UV light absorbers, conjugated aromatic molecules, hindered amine bght stabilizers, inorganic oxides or any combination thereof, preferably T1O2, Tinuvin ® famibes or any combination thereof.
- Improved light barriers have been experimentally observed for such precursors. i. Limited migration of undesired chemicals arising in the preform material to the contents of the container
- Undesired chemicals may migrate from the material of the container to the liquid in the container, such as acetaldehyde being formed in PET materials which could change the smell and taste of the liquid contents of the container.
- the present invention also aims at providing scavenging functionalities.
- the precursors comprise siloxanes or any combination thereof, preferably HMDSO or any combination thereof. Limited migration of undesired chemicals has been experimentally observed for such precursors. j. Improved internal anti-stick properties
- the precursors comprise fluorocarbons, glycols or any combination thereof, preferably PFDA, PEGMEA, CAS 116-143, CAS 116-15-4, DEGEA or any combination thereof. Internal anti-sticking has been experimentahy observed for such precursors. k. Improved direct object printability
- the precursors comprise acrylates, methacrylates, hydroxyl groups, epoxy groups or any combination thereof, preferably AA, MMA, HEMA, HE A A, GLYMA or any combination thereof.
- Improved direct printing has been experimentally observed for such precursors. l. Improved stress cracking resistance
- the precursors comprise polymer solutions, siloxanes or any combination thereof, preferably EVOH, HMDSO, VMOS, PFDA, nonene or any combination thereof. Improved stress cracking resistance has been experimentally observed for such precursors.
- the above functionalities may be desired for the complete preform or container, but may also be desired or needed only on a portion of the preform or container. Moreover, different portions of the container may be desired to have different functionalities, or a different combination of functionalities. Hence, in embodiments of the present invention, different coatings may be applied on different portions of the preform and/or container. Different coatings may be applied on different portions of the inner and/or outer preform, and/or on different portions of the inner and/or outer container. In other embodiments, the plasma coating can be deposited on at least one section or over the whole surface of the inner and/or outer preform. However, depositing the coating layer on only a portion is generally not preferred in accordance with the present invention.
- Different precursors may be deposited using a layer by layer deposition strategy, whereby in each consecutive deposition step one precursor is deposited as a layer onto at least one section of or onto the whole surface of the preform.
- Another possibility includes depositing one or more layers comprising a mixture of different precursors, whereby the deposition is achieved by introducing the different precursors simultaneously into the plasma.
- a person skilled in the art will note that any combination of the deposition possibilities mentioned in this document could be applied in order to obtain a coating with a least two different precursors.
- the functionality of the coating layer may significantly depend on the conditions, e.g. temperature and pressure, in which the coating layer is deposited. In order to obtain good functionality, it is important to work at optimal conditions, which can be different for each used precursor, although always in the preferred ranges specified in this document.
- a preform for a bag-in-container comprising an inner preform and an outer preform with facing surfaces, wherein at least one of the facing surfaces is coated with a coating layer apphed using the method as described herein.
- at least one of the facing surfaces comprises a coating layer obtainable by the method as described herein.
- the coating layer on at least one of the facing surfaces of the preform for a bag-in-container that is applied using and/or obtainable by the method as described herein is crosslinked.
- the coating layer that is applied using and/or obtainable by the method as described herein is covalently grafted onto at least one of the facing surfaces of the preform for a bag-in container.
- bag-in-container comprising an in inner container and an outer container with facing surfaces, wherein at least one of the facing surfaces is coated with a coating layer, obtainable by integrally stretching of the preform for a bag-in-container as described herein.
- the bag-in-container is obtainable by integrally blow molding of the preform for a bag-in-container.
- the use of plasma deposition for applying a coating layer for e.g. the reduction of moisture pickup provides a means to control the coating deposition process down to a nanoscale precision. Thickness control is important, because the deposition of a too thick layer could result in an ostensibly visible coating. Ostensibly visible coatings could give an impression of a faulty or contaminated preform, and are as such undesired.
- the coating may produce visible effects such as coloring or a smooth appearance. However, it is an advantage of the present invention that such effects do not appear to be the result of a coating.
- the coating layer deposited on the inner and/or outer preform may have a thickness of between 5 and 600 nm, preferably between 5 and 500 nm, more preferably between 10 and 500 nm, even more preferably between 10 and 300 nm, yet more preferably between 10 and 200 nm, still more preferably between 10 and 80 nm, such as 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm or any value therebetween, most preferably about 20 nm.
- the plasma coating thickness can be well-controlled by controlling the exposure time of the preform or container to the plasma and/or the precursors.
- the bag-in-container is obtainable by integrally stretching the preform for a bag-in-container, wherein the stretch ratio is 2-20.
- the stretch ratio with respect to volume is between 5 and 20, more preferably between 10 and 15, still more preferably between 12 and 15, such as 12, 13, 14, 15 or any value there between, most preferably about 13.5.
- said preform increases in length with a stretching ratio of 2 to 20, preferably 3 to 15, more preferably 4 to 12, even more preferably 5 to 10, and/or said preform increases in diameter with a stretching ratio of 2 to 20, preferably 3 to 15, more preferably 4 to 12, even more preferably 5 to 10.
- the length, diameter and/or volume are increased in accordance with the above-mentioned ranges.
- the thickness of the coating layer decreases with the increase of the stretch ratio. It is believed that the thickness of the coating on the preform decreases inversely proportional to the increase in surface. As the shape of the preform may change during the increase in size, the theoretical inverse proportionality of the thickness reduction to the volume stretching ratio to the power 2/3 does not necessarily hold.
- the thermoplastic preforms are stretched in length as well as in diameter during integral stretching.
- the coating layer on the inner and/or outer bag- in-container may have a thickness of 100 nm or less.
- the coating layer has a thickness of 80 nm or less, more preferably 50 nm or less, such as 20 or less.
- the thickness of the coating layer after stretching may be as low as 5 nm, but is preferably more.
- the thickness of the coating layer on the bag-in-container is 30 nm or less, more preferably 25 nm or less, still more preferably 20 nm or less, yet more preferably 15 nm or less, even more preferably 10 nm or less, such as 10 nm, 9 nm, 8 nm, 7 nm, 6 nm, 5 nm, 4 nm, 3 nm, 2 nm, lnm or any value there between, most preferably about 6 nm.
- the coating on the bag-in-container is at least 2 nm thick.
- the coated preforms and containers can be recycled well, without negatively affecting the quality of the recycled material.
- the coating layer may be applied to one or more of the following surfaces: the inside of the inner preform, the outside of the inner preform, the inside of the outer preform, and the outside of the outer preform.
- the coating layer is applied at least to the outside of the inner preform, the inside of the outer preform, or both.
- the coating layer can be applied on part of these surfaces, or on these surfaces in their entirety.
- the coating layer is applied on the surfaces in their entirety. In that way, the surface properties, such as delamination properties, but also for instance printability properties, of the inner and/or outer surfaces, of the preform or container onto which the coating layer is applied are determined mainly by the properties of the coating layer.
- the coating layer is intact.
- An intact coating layer is defined as a coating layer which covers the entire surface onto which it was applied. Therefore, the coating layer is without regions where the material of the surface onto which the coating layer was applied is exposed. In that way, the surface properties, such as delamination properties, of the preform or container onto which the coating layer is applied are determined by the properties of the coating layer.
- the coating layer stays intact during stretching of the preform, resulting in an intact coating layer on the bag-in-container.
- time of flight secondary ion mass spectrometry may be applied, as shown in figures 5-7.
- the coating layer is applied on at least a part of a surface.
- certain parts of the surface may intentionally remain uncoated.
- it is not required to coat the neck portion of a preform to be used in preparing the bag-in-container, since this neck portion normally does not deform during blow molding.
- Alternative methods of characterization of the coating layer may include optical measurements. Since a wide variety of precursors can be used to form the coating layer, optically active components such as pigments or dyes may also be incorporated into the coating layer. These optically active components may be detected using optical detection methods. For example, when fluorescent materials are incorporated in the coating layer, the presence of an intact coating layer may be demonstrated using fluorescence measurements.
- a coloring agent such as a pigment or a dye, is added to the plasma, preferably as a gas or a liquid or as a powder dissolved in a liquid or colloidal mixes in the form of an aerosol. Coloring allows an easier quality check by visible inspection, but may also be used for other visual effects.
- the presence of an intact coating layer may be demonstrated using fluorescence measurements.
- providing the coloring agent already to the plasma may provide a more even background color in an easier and faster manner than a coloring process on top of the coating.
- the coating layer is a conformal coating layer.
- a conformal layer follows the surface closely, even in case the surface comprises large curvatures, e.g. near the opening, near a neck or near the bottom of the preform or container.
- the inner preform and outer preform of a preform for a bag-in container in accordance with the present invention may be formed of the same and/or of different materials.
- the coating layer which is applied on the outside of the inner preform and/or the inside of the outer preform may prevent contact between the material of the inner preform and the material of the outer preform. In that case, the same material of the inner preform and of the outer preform will not be in contact.
- delamination properties depend on the interaction between the coating layer and the other facing surface, or on the interaction between the two coating layers.
- the coating layer may optimize delamination of the inner and outer layers of the bag-in container during and/or after blow molding.
- a preform for a bag-in-container as described herein may be formed by joining two or more superposed preforms, i.e. an inner preform and an outer preform, using methods known in the art.
- Non-limiting examples of such methods include spin welding of the inner and outer preforms, as described for instance in EP2885241.
- regions such as the neck region, where contact between the inner and outer preform is deliberately made.
- a preform for a bag-in-container wherein the same material of the inner preform and the outer preform are not in contact with each other as described hereinabove does not preclude that contact between the inner and outer preform is deliberately made in specific regions such as the neck region of the preform for a bag-in-container, in order to achieve the required structural integrity.
- Figure 1 is a schematic representation of a cross-section of a preform (inner or outer) for a container to be used in a bag-in-container according to the invention.
- preform for a container (1) comprising a coating layer (2).
- the coating layer is present on the outside of the preform.
- the coating layer may be present on the inside of the preform.
- Figure 2 is a schematic representation of a cross-section of a container (inner or outer) obtainable by blow molding of preform (1), showing container (3), comprising coating layer (4).
- the coating layer is present on the outside of the container.
- the coating layer may be present on the inside of the container.
- the coating layer as described herein may have a low surface energy.
- a coating with a low surface energy may serve different functionalities, including but not limited to reduced moisture pickup and improved delamination of the inner and outer layers.
- a coating layer with low surface energy may also be referred to as a hydrophobic coating layer.
- Preforms are often produced in one location and blow molded into containers a different location, for instance in the same location where the blow molded containers are filled. This drastically reduces the transportation volume compared to when the blow molded containers were to be transported. However, preforms may have a limited shelf-life, and after a certain period, the blow molding properties of the preform may decrease. It has been found that preforms with a coating layer with low surface energy have an increased shelf-life. This also applies to a bag-in-container having a hydrophobic coating. Low surface energy and/or hydrophobicity may be expressed in terms of water contact angle.
- the coating layer is hydrophobic.
- the preferred contact angle may be 90° or higher, preferably 100° or higher, more preferably 120° or higher, such as 150° or higher.
- the coating layer may be referred to as superhydrophobic.
- the coating layer is superhydrophobic.
- the hydrophobic coatings applied in accordance with the present invention do not have to result in a change of the color in the product.
- Such color changes are commonly observed in prior art other methods to improve shelf-life, such as the use of a scavenger or applying a water-resistant layer onto the inner and/or outer surface of a preform.
- elevated gas pressure vis-a-vis the atmospheric pressure
- the inner container, or bag delaminates from the outer container.
- the inner container delaminates from the outer container after integrally blow molding of the preform for a bag-in container in a controlled manner.
- Figure 3 is a schematic representation of a cross-section of a preform for a bag-in-container according to an aspect of the invention.
- preform for a bag-in-container (7) comprising inner preform (8) and outer preform (9), wherein the inner preform is coated with coating layer (10).
- the coating layer is present on the outside of the inner preform.
- the coating layer may be present on the inside of the outer preform.
- Figure 4 is a schematic representation of a cross-section of a bag- in-container after blow molding of preform (7), showing inner container (12), outer container (13), and coating layer (14).
- the coating layer is present on the outside of the inner container.
- the coating layer may be present on the inside of the outer container. It is also possible that after blow molding the coating layer on the outside of the inner container is in contact with the inside of the outer container. Similarly, a coating layer on the inside of the outer container can be in contact with the outside of the inner container.
- Another aspect of the invention is the use of plasma deposition for the production of a bag-in-container, said bag-in-container comprising an inner container with an outer surface and an outer container with an inner surface facing the outer surface of the inner container, wherein at least one of said facing surfaces is coated with a coating layer.
- the preforms were made by injection molding a combination of PET particles and a silver colorant, resulting in preforms having a dark greyish color. This color helped to better spot the effects of the coating.
- Preform 1 was not treated and was used as a reference.
- Preform 2 was treated with a plasma coating in accordance with the invention. During the coating process of the preform, a green pigment was added to the plasma via an aerosol.
- the preforms were subsequently inflated via the preform opening by blow stretching to a full sized bottle with a ratio of approximately 11.
- bottle 1 The reference bottle obtained from preform 1 (“bottle 1”) showed small defects near the top at the so-called “Lamello”-” area around the opening, which is a stiffened ring or series of rings, extending around the periphery of the container and which results from increased crystalhzation in the preform, and near the bottom around the injection point of the preform. Both defects are typical of the blow stretching process. Bottle 1 had a light greyish color with small intensity fluctuations near the two defects.
- bottle 2 The bottle obtained from preform 2 (“bottle 2”) showed a smooth and even light green color all over the bottle (except for the same kind of intensity fluctuations near the defects).
- the homogeneous light-green color of bottle 2 indicates that the coating remains intact after inflating the preform by a volume ratio of as much as 11.
- the color pigment is well- distributed all over the bottle and the coating adheres very well to the complete surface of the preform and bottle.
- the coating on the preform and the resulting container can serve multiple purposes. It may for instance act as a moisture barrier, which can avoid degradation of the preform during storage. It may also act as a moisture barrier for the container. Other effects include to provide color (by adding a pigment, for instance by adding it to the plasma as demonstrated in the previous Example).
- a release coating can be applied in accordance with the present invention, ensuring that an inner container easily delaminates from an outer container of a double-walled container (e.g . bag-in-container).
- the delamination is greatly reduced if the surface energy is reduced. Especially also the release is better controlled, at a predetermined pressure level.
- plasma treatments without coating tend to increase the surface energy.
- the inventors have found that the surface energy is nevertheless reduced if at least one precursor is administered in a plasma as a gas or a liquid in the form of an aerosol.
- preform 1 remained untreated, whereas preform 2 was provided with a coating according to the present invention.
- the surface energy of the preforms was tested using a set of test pens having different types of ink, each type of ink having well-calibrated surface energies. If the surface energy of the substrate is equal to or higher than the surface energy of the ink, the ink will expand on the surface, resulting in smooth and even coloring. If the surface energy of the substrate is lower than the surface energy of the ink, the ink will conglomerate in inhomogeneous droplets.
- Both preforms were subjected to three test pens, having surface energies of 34 mN/m, 38mN/m and 44mN/m, respectively. It was found that the untreated preform 1 had a surface energy of between 38 and 44 mN/m, consistent with the general assumption that PET has a surface energy between 40 and 50 mN/m, making it difficult to paint and requiring more force for delamination.
- the treated preform with a coating layer had a surface energy of less than 34 mN/m, improving delamination e.g. when producing a bag-in-container.
- the treated preform had a surface energy of less than 34 mN/m, which resulted in improved delamination when used for instance in a double-walled container (such as a bag-in-container).
- This Example shows that the surface energy can be reduced using a plasma with precursors.
- certain types of precursors may increase the surface energy of the coated surface. Such higher surface energy may be preferred to obtain other functionalities, in particular improving direct printabihty (resulting in accurate, high-quality printed images).
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Toxicology (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Details Of Rigid Or Semi-Rigid Containers (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
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Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MX2022006081A MX2022006081A (en) | 2019-11-22 | 2020-11-23 | Bag-in-container with a coating layer. |
EP20830363.6A EP4061596A1 (en) | 2019-11-22 | 2020-11-23 | Bag-in-container with a coating layer |
BR112022009763A BR112022009763A2 (en) | 2019-11-22 | 2020-11-23 | BAG-IN TYPE CONTAINER WITH A COATING LAYER |
CA3158213A CA3158213A1 (en) | 2019-11-22 | 2020-11-23 | Bag-in-container with a coating layer |
CN202080090783.0A CN114981053A (en) | 2019-11-22 | 2020-11-23 | Bag-in-container with coating |
JP2022529677A JP2023503308A (en) | 2019-11-22 | 2020-11-23 | Bag-in-container with coating layer |
US17/777,132 US20220401992A1 (en) | 2019-11-22 | 2020-11-23 | Bag-in-container with a coating layer |
AU2020387532A AU2020387532A1 (en) | 2019-11-22 | 2020-11-23 | Bag-in-container with a coating layer |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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NL2024296 | 2019-11-22 | ||
NL2024296A NL2024296B1 (en) | 2019-11-22 | 2019-11-22 | Bag-in-container with a coating layer |
Publications (1)
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WO2021101385A1 true WO2021101385A1 (en) | 2021-05-27 |
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PCT/NL2020/050736 WO2021101385A1 (en) | 2019-11-22 | 2020-11-23 | Bag-in-container with a coating layer |
Country Status (10)
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US (1) | US20220401992A1 (en) |
EP (1) | EP4061596A1 (en) |
JP (1) | JP2023503308A (en) |
CN (1) | CN114981053A (en) |
AU (1) | AU2020387532A1 (en) |
BR (1) | BR112022009763A2 (en) |
CA (1) | CA3158213A1 (en) |
MX (1) | MX2022006081A (en) |
NL (1) | NL2024296B1 (en) |
WO (1) | WO2021101385A1 (en) |
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-
2020
- 2020-11-23 EP EP20830363.6A patent/EP4061596A1/en active Pending
- 2020-11-23 AU AU2020387532A patent/AU2020387532A1/en active Pending
- 2020-11-23 MX MX2022006081A patent/MX2022006081A/en unknown
- 2020-11-23 JP JP2022529677A patent/JP2023503308A/en active Pending
- 2020-11-23 CN CN202080090783.0A patent/CN114981053A/en active Pending
- 2020-11-23 CA CA3158213A patent/CA3158213A1/en active Pending
- 2020-11-23 US US17/777,132 patent/US20220401992A1/en active Pending
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BR112022009763A2 (en) | 2022-08-30 |
US20220401992A1 (en) | 2022-12-22 |
CN114981053A (en) | 2022-08-30 |
EP4061596A1 (en) | 2022-09-28 |
CA3158213A1 (en) | 2021-05-27 |
JP2023503308A (en) | 2023-01-27 |
AU2020387532A1 (en) | 2022-06-02 |
MX2022006081A (en) | 2022-06-14 |
NL2024296B1 (en) | 2021-08-23 |
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